Process for resolving petroleum emulsions



I Patented Dec.

i T D S TES PATENT arm: I i 4 I mocnssron nizi fiw rn'raoLnUM it i EMULSIONS Melvin ne Groote, University City, and Arthur F; Wirtei, Klrkwood, Mm, assignors, by mesne asvsignments, to Petrolite Corporation, Ltd., a cor- 1 poration of Delaware I No Drawing.v Application December 21, 1 938,

, Serial No. 247,002 7 I g I o n 7 Claims;

This invention relates primarily to the treatment of emulsions of mineral oil and water, such as petroleum emulsions, for the purpose of separating the oil from the water.

One object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oll type. that are commonly re- 'ferred to as cut oil," roily oil," "emulsified oil,"

,etc., and whichcomprise fine droplets of. natu-' rally-occurring waters or brines dispersed in a more or less permanent state throughout the oil 'which constitutes the continuous phase of the emulsion.

Another object of our invention is to provide an" economical and rapid process for separating J emulsions which have been prepared under controlled conditions frommineral oils, such as crude I vpetroleum and. relatively soft waters or weak brines. Controlled emulsiflcation and subsequent demulsification under the conditions just mentioned is'of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

The demulsi'fyingagent employed in our process is a new compound or composition of matter consisting of a certain kind of salt derived from ;a surface-active esterified amine of the kind hereinafter described and an alkylated naphthalene sulfonic acid of the kind in which. there is at least one alkyl group substituted in the naphthalene nucleus, the said alkyl group or groups in three carbon atoms and not more than ten carbon atoms.

Said "alkylated sulfonic acid can be described by the following formula:

o more) v v in which n indicateSany small 'whole number,

V as 1,!2, 0r 3; but generally speaking, the

-40 monosulfonic acid would be employed, and for purposes of brevity,- the formula -D.SOaH will-}be p It is well known that certain monocarboicy organic acids containing approximately eight car- 45 bon atoms or more and not more than 32 carbon atoms; are characterized by the fact that they combine-with alkalis to produce soap or soaplike materials. 'These detergent-forming acids include fatty cids, halogenated fatty acids, resin '50 acids, hydrog nated resin acids, petroleum acids,

venience. these turn being characterized by containing 3 at least chlornaphthenic 'acids,'etc. Forjsake of conacids will be indicatedby'the v formula R.COOH. j Itis known that basic compounds may be pro duced from detergent acids, or esters thereof, and 5 monoalkylolamines, such as. monoethanolamine;

' which are characterized by the following formula:

acoaommm 1 Similarly, one can produce materials of the type 6 I indicated by the following formulas:

(acooLcmo-zNH (Rhcoocim) 3N Needless to say, in the above formulas where an amino hydrogen atom appearait may be replaced l5 1 by some suitablesubstituent; such as an alkyl- 'radical,* alicyclic radical, etc. Such amines, containing the esterified detergent-forming acid radicaL are surface active in either hydrophobe v or hydrophile solvents, 'andespeciallyafter new 20 tralization with acids such asv HCl.

Ifa surface-active amine of the kind above described is'used to neutralize an alkylated aromatic acid of the kind typified by the formula D.SO:;H,

then one obtains complex saltsicharacterized by having both a surface-active anion and a surface- =active'cation; and these salts may be'illustrated by' the following formulas:

' moooimmnnsogn v so The actual composition of the. above type of -material may be'more clearly expressed by-the following formula which is another form of the particular preceding formula, in which an esterlfied primarybasic amine'isemp'loyed for neutralization: I

. y H A g I I [RCOQCzHdfiIH sow Having indicated in a generalway the'nature cf the: vcompound or compositionof matter employed as the demulsifier in ourprocess; it is deemed desirable to indicate the method of prov One can obtain or manufacture chemical compounds who'se composition is indicated by the following formulas:

However, the radical C2H4, which appears in the above formula, may represent any similar radical, such' as a C3Ha radical, a C4H8 radical,

etc., and therefore, the above formula may be indicated as follows:

acoocmh), I

NUT)..."

oH.c,H,,

in which R.COO represents the oxy-acyl radical derived from a monobasic detergent-forming acid; T represents a hydrogen atom or a nonhydroxy hydrocarbon radical, or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than eight carbon atoms; 11. represents a small whole number, which is less than 10; m represents the numeral 1, 2, or 3; m' represents the numeral 0, 1, or 2; and 112." represents the numeral 0, 1, or 2, with the proviso that m+m'+m" equals 3.

In the above formulas it has been pointed out that T represents a hydrogen atom, or a nonhydroxy aliphatic hydrocarbon radical, such as a methyl radical, ethyl radical, propyl radical, amyl radical, octadecyl radical, etc. However, T may also represent a non-hydroxy alicyclic radical, such as a cyclohexyl radical or a non-hydroxy aralkyl radical, such as a benzyl radical; or T may represent the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical, or the equivalent thereof, by the acyl radical of a monobasic carboxy acid, such as acetic acid, butyricacid, heptoic acid, or the like; all of which. are characterized by having less than eight carbon atoms. The alkylol radical prior to acylation may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided the hydroxy radical is attached to the aliphatic residue of the aralkyl radical. v

In the above formula, as has been pointed out, R.COO represents the oxy-acyl or acid radical derived from the acid RCOOH. R.COOH represents any monobasic detergent-forming car-boxy acid, such as a typical fatty acid or abietic acid or naphthenic acid. 4

Typical fatty acids are those which occur in naturally-occurring oils and fats, and generallyhave eight or more carbon atoms and not over 32 carbon atoms. Common examples include oleic acid, stearic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid, palmitic acid, myristic acid, etc. producesoap or soap-like materials, and are commonly referred to as being monobasic detergentforming carboxy acids.

The alkylol radical, previously referred to, prior to esterification, may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided the hydroxy radical is attached to the aliphatic residue of the aralkyl radical.

As to the amines above described, which happen to be tertiary amines, it may be well to point out that these may be formed readily by a reaction involving an ester of the selected detergentforming acid, for instance, a fatty acid ester, such as the glyceride, and a corresponding amine. This may be illustrated in the following manner:

' oH.c,n.N

OH.C|H|

(I) 11.000 011mm acoomm R.COOC:H; onclrrr-N '3' '0H.C;HN+C:H;(OH)= 12.000 011cm. 011cm.

OHLCrHc omega-N OH-CIHI OELCHHA 11.000 ZZ'Z' LR'COCPCH' 011.02 acooioin R.c .7 (11) R000 omega-N -a R.COO.C:H|-N+2CiHs(OH)= R-(jOO-CIE 3:22: 3.000

OH.C:H4+N

. OH.Ca 4

ILCOO These acids combine with alkali to Reference is-made to co-pending application rcr patent Serial No. 180,993, flied December 21, 1937, by Melvin D'e Groote, Bernhard Keiser and Charles M. Blair, Jr,

If triethanolamine, employed in the above, formula; is replaced by ethyl diethanolaminep, then one would obtain one of the remaining types I aaaasaa of tertiary amines illustrated. Reference is made I t Patent No. 2,167,349, dated July 25; 1939, to

De Groote', Keiser, and Blair.

In the remaining type of material there is amino hydrogen atom present. The manufacture of such material may be illustrated by the is following reactions:

r I OHCiH I .However, if maximum yields are not necessary, one need not resort to reactions ofthe'kin'dpre viously described'to produce secondary amines, but one may employ the following type of reac- Suitable primary and secondary amines, which may be vemployed to produce materials of thekind 'J methyl ethanolamine, propanolamine, diproabove described, include the following: diethanolamine, monoethanolamine, ethyl ethanolamine,

panolamine, pro'pyl propanolamine, etc; Other examples include cyclohexyloiamine, dicyclohexylolamine, cyclohexyl 'ethanolamlne, 'cyclo .hexyl propanolamine, 'benzylethanolami ne, benzylpro'panolamine, pentanclamine, hexanolamine,

hexanolethanolamine, etc.

Itis also known thetyiie;

that one may have amines of cum canon cnno clmon' Y 0.11.00.11.01:

n-cimocimon' n-cimocimon, n-cimon cnnocnnon canon canon Canto CaH4OH 'CaHtOCrHaQH cirnocimo'rr \mmon mNclrnocmlon Such amines may serve a's'the obvious functional equivalents of the previously described aminesand which are free from an ether linkage.

All of the amines of the kind above described and characterized by the formula: 1

haveiour common characteristics. In the first s t place, these. amines are not quaternary ammonium basesor salts thereof. The expression quaternary ammonium" is properly and con octylethanolamine;octadecylethanolamine, cyclo- ,Similarly, suitable tertiary amines which may be employed include the following: triethanolamine, diethanolalkylamines, such as diethanol ethylamine, diet'hanol prop'ylamine', etc. Other examples include dlethanol, methylamine, tripropanoiamine, dipropanol methylamine, cyclohexanol diethanolamine, dicyclohena'nol ethanolamine, cyclol1exyl diethanol'amine, dicyclohexyl ethanolamine, dicyclohexanol ethylamine, benzyl diethanolbenzyl dipropanolamine,- tripentanolamine, trihexanolamine, hexyl" ethanoiamine,. octadecyl diethanolamine, polyethanolamine, etc.

a st be recognized is, that these amine com-' the mmpounds used as ventionaliy applied 'to compounds in which all four hydrogen atoms of the ammonium radical NH4 have been replaced by a hydrocarbon radical or, oxy-hydrocarbon radical, as, for example, in t'rimethyl phenyl ammonium hydroxide.

Secondly, an important characteristic which pounds are not amides. It is to be noted that an ,amide formation involves a product in which, there is a direct linkage between'the' carbox'ylic carbon atom and the nitrogen atom in the amine. This-is not the casein-the compounds employed as intermediate rawmaterials for production of dem i s agents in the present process. Y r Y In the third place, it must be recognized that these compounds are derived only. from basic amines.

The'word basi6-is employed .to excludetamines having little or no baslcity, such as,

the ordinary aromatic amines, or any amine having at "least one aryl radical directly joined to the amino nitrogen atom. For this reason, these amine prpducts which are herein-contemplated as demulsiiying agents, and which necessarily are characterized by freedom )i'rcm anyjnryl groups as such, cannot be 'derived from ar'yl amines. They are derived solely from alkyl, alicyclic, or aralkyl amines':havin'g at least onehydroxyl group present. It is truethat in the aralkyl amines there is an nryl group present, but'it is not directly attached to the nitrogen-atom, as

in the case of aryl amines, but in fact, represents nothing more or less than a substituted albiamine. For instance, we consider benzylamlne as being the primary amine, phenmethyl amine.

Finally, it must be recognized ,that these ma-, terials have not lost any basicity in the forms of the esterified' amine, and that they exhibit all the properties of a basic amine, that is," they com-,

blue with water to form a base, presumably a substitutedammonium compound, but not quaternary ammonium compound, insofar that there are always one, two, or three unsubstituted hydrogen atoms of the ammonium radical present. They combine with various acids to form salts. For example, they may be combined with acetic acid, hydrochloric acid, lactic acid, chloracetic acid, nitric acid, butyric acid, phosphoric acid, oxalic acid, or any suitable organic or inorganic acid, to form salts.

Reference is again made to the formula which summarizes the various amines used as intermediate raw materials, viz.:

in which the characteristics have their previous significance. Attention is directed to the fact that where the substituted alkyl radical OH.R.COO.CH-

appears, a suitable non-aryl radical other than an aliphatic residue may serve as the functional equivalent; for instance, an 'alicyclic radical derived from a cyclohexyl radical, or an aralkyl radical derived from a benzyl radical. In other words, in the hereto appended claims references to the C1121: radical as such,.or as an alkyl radical or residue, is intended in the broad sense to include the alicyclic radicals or residues, or the I aralkyl" radicals or residues which are the equivalent thereof. There is no intention to include an aromatic radical where there is a direct linkage between the aromatic nucleus and the amino hydrogen atom, for the reason that such products have little or no basicity and do not have the characteristic properties of the amines previously described.

amines of the non-aryl type which may be employed to produce the amine contemplated as the.

then-it is understood that such materials would not represent a hydroxy tertiary amine within the meaning orscope, as herein employed., If, on the other hand, triethanolamine were treated In indicating the various hydroxylatedtertiary with lactic acid. so as to give monolactyl triethanolamine of the following composition:

on o

cmonc-o-Cuzn .onolm-n oncln,

' then such compound would be included, due to the presence of one or more hydroxyl radicals attached to the alkyl radicals.

Similarly, in indicating the various, hydroxylated primary or secondary amines of the nonaryl type, which may be employed to produce the amine contemplated as the demulsifying agent of the present process, it is desirable to indicate that amines-of the type where a hydroxy acyl radical replaces a hydrogen atom of the hydroxyl radical of a. hydroxy primary or secondary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, if ethanolamine is treated with lactic acid so as to form the lactyl derivative of the following formula;

- on o then it is understood that such materials would not represent a hydroxy primary amine within the meaning or scope, as herein employed. The same would be true if thelcorresponding product were derived from diethanolamine, provided both hydroxy radicals had been esterified with lactic acid. f

The manufacture of compounds from tertiary amines is relatively simple, because no precautions are necessary to prevent amidification. The selected detergent-forming acid, or ester, as, for example, a fatty oiland the selected hydroxy tertiary amine, are mixed in' suitable proportions and heated at some point above the boiling point of water, for instance, 110 C., and at a point below the decomposition, point of the amine or the fatty oil, for instance, 180 C., for a suitable period of time, such as two to eight hours. Mild agitation is employed. A catalyst, such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about one-half of 1%, or less. It is noted that the fatty acids'are employed in this instance, in the form of an ester, to wit, the glyceride, although, as previously pointed out, other functional equivalents can be readily employed with equal facility. It is to be noted that the reactions above described do not take place to any appreciable extent if the fatty acid has been converted into the soap or salt. Such salts are not functional equivalents. As

previously indicated, an ester of abietic acid or naphthenic acid might be employed, if desired.

When, however, one is employing a hydroxy secondary amine, precautions must be taken, so that one gets a substantial percentage of products derived by esterification, rather than amidification. Anysuitable ester may be employed, but it is often most convenient to employ the glyceride of a fatty acid, for instance, triricinolein. The selected glyceride and the selected hydroxy secondary amine are mixed in suitable proportions and heated at some point above the 'boiling point of water, for instance, 110 C., and below the decomposition point of the amine or fatty material, for instance, 180 0., for a suitable period of time, such-as 4-24 hours. Mild agitation is employed. A- catalyst, such .as sodium oleate, sodium carbonate, caustic soda, etc., may

is to be noted that the fatty acids are present in ester form and not in the form of the free acid,

and thus there is no'tendency to form the salt employedis two moles of the described.

to any marked extent; and if conducted at the lower range of reaction temperatures, there is a.

decided tendency to form the esterification' products, rather than, the amidiflcation products.

In order to illustrate suitable examples of the amines which maybe used as intermediate raw materials for neutralizing alkylated naphthalene directed tdthe following examples: I Intermediate amine 'E'x ample -1 Castor oil is employed. For the sake of convenience, its molecular weight isconsidered as being 925. Commercial triethanolamine and sulfonic acids of thekind described,- attention is castor oil in the proportion of one mole of castor -oil and three moles of triethanolamine are heated to a temperature between *150-180 C. for, two

hours. Mild agitation is employed. Intermediate amine Example? The same procedure is followed as'in Intermediate famineExample 1, except that the ratio moles of triethanolamine. 1 Intermediate amine Example 3 The same procedure is employed as in Intermediatelamine Example 1, exceptthat the ratio employed is three moles of castor oil to three moles of triethanolamine. as

Intermediate amine Eaample 4 One mole of methyl naphthenateis reacted in the mannerpreviously cule oi triethanolamine.

Intermediate amine Example 5 Diethanolamine is substituted for triethan'olamine in-Example 4. v

Intermediate amine Example .6 Methyl abietate is substituted 'for methyl rfaph- Intermediate amine Example 7 v Olive oil is substituted amples 1, 2,'and 3 above.-

Intermediate amine Example 8 Ethyl diethanoiamine' is substituted for triethanoiamine in 1 Intermediate amine Example!) preceding.

' Intermediate amine Example 10 B enzyl diethanolamine is substituted for ethyl diethanolamine in Example 8 above.

- Intermediate amine Example 11" f Castor oil (triricinoleinl is employed. "Fer convenience its molecular weight is considered n as being 925.v Commercial diethanolamine and castor oil in the proportion of one'mole' of castor oil to threemolesof diethanolamine, are heated to a temperature of 120440 0., for about twelve hours. Mild agitation is employed. Loss of ,basicity is an indication of amidification. Time of. esteriiication may be extended or temperature castor oil to three.-

described with one molefor castor oil in Ex-.

Examples 1,'and 2, previously as-suitable as another-dorm.

lowered or raised, so as to insure maximum esteriflcation, and particularly, so as to produce a product characterized by the presence of one unty by means of a conventional esteriflcation proc 1 nitrogen.

Intermediate amine Eramplelz In the previous examples wherecastor voilis employed, blown-castor-oil is substitutedtherefor. We prefer to use a'drastically oxidized castor oil having, approximately the following charv acteristics: 1 Acid number 13.2 to. 25.0 saponiflcation number 230.5 to,274.0 Iodine number 43.5 to 55.0 Acetyl number 164.0 to 192.0 'Hydroxyl value 188.0to 220.0 Percent unsaponiiiable matter .1-.1 Percent nitrogen 0.0 Percent $03..........'..... 0.0 Percent ash Trace I In employinga drastically oxidizedcastor oil, it is our preference to eliminate carboxylid'acidbess. For instance, in referring to the analyses of the blown oil above, itwill be seen that such product contains acidity equivalent to -10% of the total saponiflcation value. Such acidity can be removedby esteriflcation with an alcohol,

such as methyl alcohol, ethyl alcohol, propyl al- COhOl, etc. Qn'the other hand, insofar that glycerine is the .naturally occurring alcohol present in'most oils and fats, and alsoinsofarf erence to add suflcient glycerineto such blown that glycerine is non-volatile, it is our prefoiland keep it agitated to a temperature of approximately 125-170 C., untllcarboxylic acidity disappears. .Such neutral or completely ester- ,fled blown oil is then employed in manufacturing the intermediate amines of the kind above described.v

Reference is made to the co-pending applications' Serial No. 180,992, filed December 21,1937, 'by Melvin De Groote, Bernhard Kelserand- Charles M. Blair, Jr.;- Serial No. 202,986, filed April 19, 1938, by Melvin'De Groote, Bernhard Keiser and CharlesM. Blair, Jr.; and Serial No. 208,220, filed May 16,4938, by Melvin De Groote, Bernhard Keiser and Charles M. Blair, Jr.

7 I It has been previously pointed out thatthe. intermediate. amines are characterized'by'the fact that they combine withacids to form salts;.

for instance, they'willcombine with acetic acid,

hydrochloric acid, sulfuric acid, etc. In the present instance, of course, "they are employed to form salts, but only aparticular kind of salt,

towit, the one derived by neutralization of an alkylated naphthalene described. 'One isomeric cm of an amine is onic acid or the kind .Alkylated naphthalene sulfonicacids are pro- -duced commercially, and the salts are used for a varietyto'f purposes. They are generally produced from naphthalene, because there does not appear to be any advantage in the use of' a-'.

naphthalene derivative, such as chlor-naphthalene, alpha and beta naphthol'. etc. -Inother words, one could introduce the sulionic acid residue and the alkyl residuesinto a substituted naphthalene, such as chlor-naphthalene, etc.,

Just as readily, perhaps, as in the-case of naph-e thalene. Suchfsimple derivatives, of course, are

the chemical equivalent tat-naphthalene in the manufacture of Such .sulfonic acids as are em:

70 cohol.

ployed in the manufacture of the present reagent. It is understood that the word naphthalene is hereinafter employed to include these derivatives.

The general process of manufacturing the particular salts used to produce the de'mulsiiler employed in our process, consists in converting the naphthalene into either the alpha or beta naphthalene sulfonic acid, or a mixture of the? same,

or in some instances, into a dior even a trisulfonic acid, or a tetrasulfonic acid, or a mixture oi the various types. In most instances, there is no advantage in introducing more than one sulfonic acid residue. In many instances, it

is unnecessary to use particular care to prepare either only the alpha sulfonic acid, or either only the 'beta sulfonic acid, because "a mixture in which either one.or the other predominates, or

a mixture in which the alpha and beta sulfonic' acids are present in. approximately equal amounts, is just as satisfactory as one sulfonic .acid completely freed from the other type.

.The alcohol employed, such as propyl alcohol, a butyl alcohol, an amyl alcohol, a hexyl alcohol, a decyl alcohol, etc., is converted into the acid sulfate, such as propyl hydrogen sulfate. The naphthalene sulfonic acid and the alkyl hydrogensulfate are combined in proportions so that one, two, three, or even four alkyl groups are introduced into the aromatic residue. This condensation reaction is generally carried out in the presence of an excess of sulfuric acid. In some instances, the various reactions, such as sulfonation, sulfation, condensation, etc., are carried out simultaneously. Generally speaking, the dialkylated and tri-alkylated material appear to yield the most desirable type of reagent. Thepresence of some mono-alkylated material,

or some tetra-alkylated material is not objec- 40 tionable, and may even be desirable.

It is obvious, of course, that the alkylated groups introduced might be derived from olefines, such as butylene, propylene, amylene, etc., insofar that such olefines react directly with sulfuric acid, to produce the alkyl hydrogen sulfates. Of course, in addition to introducing such alkyl residues of the kind described, into the aromatic nucleus, one could also introduce an alkyl residue from some other alcohol, as, for

example, an alkylated group derived from ethyl or methyl alcohol, or one might introduce a group derived from an aryl, aralkyl cyclic, or hydroaromatic alcohol, or the like, but regardless of whether or not one introduces suchother residues, it is necessary that at least one alkyl residue of the kind described, 1. e., having at least three carbon atoms and not more than ten carbon atoms, be introduced into the naphthalene ring. Such compounds having some other 0 group present, such as -methyl group, might be considered as being derived from methyl naphthalene, instead of naphthalene, and thus, would fall within the class of chemical equivalents previously noted.' It is immaterial as to the particular alcohol'employed, or the particular isomeric form of the alcohol employed, although generally speaking,it is most desirable to use the one lower in cost. It is immaterial whether one uses normal propyl alcohol or isopropyl alllt is immaterial whether one uses a normal butyl or isobutyl alcohol. It is immaterial whether .the alcohol be a primary alcohol,

75 It is obvious that a large number of isomers can be produced in the manufacture of the reagent employed as the demulsifier in the present process. For instance, although the sulfonic pyl alcohol, normal butyl alcohol, isobutyl al-- 15 cohol, and amyl alcohol, it is our preference to produce our reagents from these acohols, and in some instances, it is desirable to introduce different alkyl groups, such as a propyl group and butyl group, into the'same sulfo-naphtha- 20 lene residue. I

In the actual manufacture of alkylated naphthalene sulfonic acids, the composition of the desired chemical reaction is followed by a washing process which removes the excess of sul- 25 furic acid or other sulfonation, sulfation, or condensation reagent employed. The acidic mass thus obtainedis neutralized in any convenient manner with any suitable base, such as ca'ustic soda, caustic potash, ammonium hydroxide, and 36 the like. However, in accordance with what has been said herein, the acidic mass is neutralized with the amine of the kind previously described.

moleculeof naphthalene by the customary sulfa- 45 tion, sulfonation, and condensation reactions.

The resulting mixture consists, largely of dipropyl naphthalene sulfonic acids and tri-propyl naphthalene sulfonic acids, with possibly small amounts of mono-propyl sulfonic acids and tetra- 50 propyl sulfonic acids present Generally speak- -ing, it is easier to conduct the reaction so that thebulk of the sulfonic acid represents the beta type, although the alpha type may be produced, if desired. The product is neutralized with a com- 55 plex amine of the kind typified by Examples 1,2,

3 or 12, previously described. The product so obtained is diluted with one or more solvents, so

as to reduce its viscosity to that of ordinary castor oil, or slightly greater. The solvents which we 60 preferably employ are a'mixture of two or more of the following: Water, denatured alcohol, kerosene, or tar acid oil.

Amongthe reagents which are particularly effective are the salts formed by reaction between 65. amines of th kind exemplified by Examples 1-12,

inclusive, above, and the following alkylated naphthalene sulfonic acids, i. e., mono-isopropyl naphthalene sulfonic acids, di-isopropyl naphthalene sulfonic acids, tri-isopropyl naphthalene sulfonic acids, mono-normal butyl naphthalene sulfonic acids, di-normal butyl naphthalene sulfonic acids, mono-isobutyl naphthalene sulfonic acids, di-isobutyl naphthalene sulfonic acids, mono- ,amyl-napht-halene sulfonic acids, di-amyl naphthaiene sulfonic acids, tri-aniyl naphthalene sulfonic acids, monohexyl naphthalene sulionic acids, di-hexyl naphthalene suli'onic acids, tri-' .hexylnaphthalenesulfonic acids. mono-octyl 5 naphthalene sulionic acids, di-octyl naphthalenesulfonic acids, 'mono-decyl naphthalene sultonic I acids, di-decyl naphthalene sulionic acids, monoisopropylv di-normal butyl naphthalene sultonic.

acids, di-isopropyl di-ncrmal butyl naphthalene naphthalene su'lfonic acids, etc.

- In such instances where there is present more thanone'sulfonic acid radical, as in'the formation oi. a disuli'onic acid, or a; trisulfonic acid, or a tetrasulfonic acid, ii desir'ed, allth'e sultonic sulfonic acids, di-isopropyl mono-amyl naphthalene sulfonicacids, mono-isopropyl mono-hexyl radicals may be neutralized wlthamines oi! the kind previously described, or some of the sulionic acid radicals may be neutralized with some" other 20 suitable base, 'such as a sodium hydroxide, potassium hydroxide, ammonium hydroxide, etc., provided that at least one 'sulfonlc acid radical has been neutralized by amines or the kind previously described, f

7 Conventional demulsii'ying agents employedfin the treatmentot oil fleld emulsions are used as such, or after'dilution with any suitable solvent, such; as water, petroleum hydrocarbons, such as gasoline, kerosene-stove oil, a coal tar product, such as benzene, toluene, xylene, tar acid oil,

ores o1, 'anthra'cene. oil, etc. Alcohols, particu'-; larly aliphatic alcohols, such as" methyl alcohol, ethyl alcohol, denatu'red'alcohol, propyl alcohol,

butyl alcohol, hexyl alcohol, pctyl-alcohohetc,

may be employed as diluents. Miscellaneous-sob tion, rather than the formation of a. substituted amide,- or the formation of an'imide or substiboth oil andwater solubility; 'Sometimes they tuted lmide. Such obvious departurefrom conventional nomenclaturehas been for purposes of simplicity and to show the similarity between certainreactions. I

It is well known that conventional demulsifying agents-may be used in a water-soluble form, or man oil-solubleform, or in a form exhibiting may be used in aiorm which exhibits relatively limited water solubility and relatively limited oil solubility. However, since such reagents are sometimes used-in a ratio of 1 to 10,000,;or 1 to 20,000,.or even-1 to 30,000, such an apparent insolubility in ,oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same factis true in regard to the material or materials employed as the demulsifyingagent of our process.

vents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material orimaterials employed as the demulsiiying agent of'our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsiiying agents. Moreover, said material or materials may be used alone or inadmixture with other suitable well known classes of demuisifying agents, such as demulsiiying agents of the modi- I fled fatty acid type, complex amine type, the petroleum sulfonate type, the alkylated suli'o-aromatictype, neutralized in the conventional man:

ner,'or evenun-neutralized. Incidentally, neutralization oi. the" alkylated sulfonic acidwith the complex amine need not necessarily take place in. stoichiometrical rela? tionship, but one may employ an excessot the sulfonic acid or or the amine. Incidentally, salts made by direct neutralization, but of course can -'be producedfju'st as eflectively by some other means. For instance, a double decomposition reactionmay be, utilized, i. e., the amine hydrochloride and the sodiumor potassium salt of the sulionic acid might each-be dissolved ina hydrophobe solvent, such as an alcohol and mixed with or the kind'herein contemplated need not be has been indicated previously, in essence, We have discovered that if a suitable alkylated naphthalene sulfonic acid is neutralized with an amine of the kind described, one obtains an unusual reagent, to wit, one characterized by having both a surface-active anionand a surface-active cation;

and we have .furthermore discovered that such reagent is of unusual efiectiveness for breaking oil fiel'd'emulsions. As far as demulsification is con 'cemed, there does not appear to be any suitable explanation of this unusual superiority; and similarly, there does notseen to be any basis by which one could anticipate'or foresee this unusual effectiveness. Apparently, thismarked improvement -35 is not directly related to oil or water solubility, insofar that. similar neutralization with other amines may yield .compounds .which have a greater solubility' in oily materials orin water, "and yet are not nearly as suitable and not nearly nearly as marked improvement over the correspending sodium ammonium salts, and in many cases it'might even be said that .a product is 50 1 obtained which is inferiorto the conventional sodium or ammonium salts. Apparently this in-- dicates that the increased value doesnot reside stance, aniline, toluidine, propylamine, diamyl the separation or sodium or potassium chloride.

" which could be filtered ofl! andthe alcohol evaporated, -so as to leave theamine' salt of the kind I to produce the chemical compound, Previously.

described, happened to .be neutralized with atdesired. Attention is directed-to the i'act that the word .amidiflcation has been applied to the reaction involving the-replacement oi' amine hydrogen atom byan acyl radical, without conventional" Ji m itgt ion toa reactioninvolvfing ammonia. The

replacement of the amine hydrogen atom or a v 'primaryamine or asecondary amine by an acid radical, has been considered as'being tained. In other words,.i.f the same alkylated 65 'ionic acids, such as. certainones derived i'ro m fl; t

in the additive effect in all instances or the amine residue per se. Furthermore, the .efi'ec--- tiveness of the complex amines is not enjoyed by various other amines-which at least bear some superficial analogy to the complex amines, although they are not surface-active. For inamine, triamylamine, etc.,-cannot be substituted for the amines employed for neutralization in the preceding examples, without detracting markedly from the value of the compounds obnaphthalene sulforiic' acids" which are employed least-certain other amines, such as those referred to, oneapparently-does not obtain a reagent of 7 any marked value, and especially a -reagent or any superiority or efiectiveness i'or' demulsii'y- 'ing on iieldjemulsions.v Similarly, the applicants have experimented with a number of other sulpetroleum, and found that neutralization with amines of the kind herein described does not give nearly as effective a reagent, in many instances, as conventional neutralization with caustic soda, caustic potash, ammonium hydroxide,

and the like. Based on the results of actual tests obtained in a variety of emulsified crudes occurring in a number of the major. oil fields of the United States, the conclusion one must inevitably reach is, that the result obtained by uniting the two surface-active residues, 1. e., the amineresidue of the kind described and the sulfa-aromatic residue of the kind described, in a single molecule, is an unlocked-for unique quality which could not be foreseen by the present knowledge of the art and which produces a demulsifying agent that is particularly eflective for a large number of emulsified crude oils.

It is obvious that certain functional equivalents may be employedi'for instance, hydroxyamines characterized by the presence of a cyclohexyl radical, may be replaced by those in which an alkylated cyclohexyl radical appears. Simiof the .kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various;ways or by any of the various apparatus now generally used to resolve or. break petroleum emulsions with a chemical reagent, the aboveprocedure being-used either alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a product of the kind derivable by neutralization reaction between (A) a surface-active amine of the formula type in which R.COO represents the oxy-acyl radical derived from amonobasic detergent-forming acid; T represents a hydrogen atom or a nonhydroxy hydrocarbon radical or the acylated radical obtained by replacing-a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid H having less than eight carbon atoms; n represents a small whole number which is less than 10; 112 represents the numeral 1, 2, or 3; m represents the numeral 0, 1,'or 2;. and m" represents thenumeral 0, 1, or 2, with the proviso that m+m'+m" equals '3; and (B) a surface-- active alkylated naphthalene sulfonic acid in which at least one alkyl'group substituted in the "naphthalene nucleus contains at least -three carbon atoms and not morethan 10 carbon atoms.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subiecting the emulsion to the action of a demulsifying agent comprising'a product of the kind derivable by neutralization reaction between (A) a surface-active amine of the formula type in which R.COO represents the oxy-acyl radical derived from a fatty acid having at least 8 and not more than 32 carbon atoms; T represents a hydrogen atom .orv a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an -alkylol radical by the acyl radical of a monobasic carboxy acid having less than eight carbon atoms; n represents a small whole number which is less than 10; m represents the numeral 1, 2, or 3 m represents the numeral 0, 1, or 2; and m" represents the numeral 0, 1, or 2, with the proviso that m+m'+m" equals 3; and (B) a surfaceactive alkylated naphthalene sulfonic acid in which at leastone 'alkyl group substituted in the naphthalene nucleus contains at least three carbon atoms and not more than 10 carbon atoms.

I 3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a product of the kind derivable-by neutralization reaction between (A) a surface-active amine of the formula type (R.o00.o,.Hz.)..

v Nov) in which R.COO represents the oxy-acyl radical derived from a fatty acid having at least 8 and not more than 32 carbon atoms; '1' represents a hydrogen atom or anon-hydroxy hydrocarbon radical or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than eight carbon atoms; n represents a small whole number which is less than 10; m represents the numeral 1, 2, or 3; m represents the numeral 0, 1, or 2; and m" represents the numeral 0, 1, or 2, with the proviso that m+m'+m" equals 3; and (B) a sur-' face-active alkaylated naphthalene monosulfonic acid in which at least one alkyl group substituted in the naphthalene nucleus contains at least three 'carbon atoms and not more than 10 carbon atoms;

in which R.COO represnts the boxyacyl radical derived troma fatty acid having at least 8 and not more than 32 carbon atoms; T represents a hydrogen atom or a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacinga hydrogen atom ofthe hydroxyl group of an alkylol radical by the acyl radical of a-monobasic carboxy acid having less than eight carbon atoms; m represents the numeral 1, 2, or 3; m

represents-the numeral 0,- 1, or 2; and m" represents the numeral 0, 1; or 2, with the proviso that 1n+m'+m" equals 3; and (B) .a-suriace-active alkylated naphthalene monosulfonic .acid in naphthalene nucleus contains at least three carbon atoms and not more than 10 carbon atoms.

ing the emulsion-to the action of a demulsi1ying agent comprising a product oi the kind derivable by neutralization reaction between (A) a surfaceactive amine of the formula type (R.CO0.C1H|)- v 1. (H.CzH4)-' in which R.COO represents the oxy-acyl radical derived from a Iatty'acid having at least 8 and not more than 32 carbon atoms; m represents the numeral 1, 2, or 3;and vm represents thenumere] 0, 1, or 2; with the proviso that m-i-m'=3; and (B) a surface-active alkylated naphthalene monosulfonic acid in which at least one alkyl group substituted in the naphthalene. nucleus contains at-leastfthree carbon atoms and' not more than carbon atoms.

6. A process-for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsiiysurface-active amine of the formula type m ce 0.0m.)

nhich at least one alkyl group substituted in the aderived from a fatty acid having 4? least 8 and not more than 32 carbon atoms; 1!: represents the in which R.COO represents the oxy-acyl radical numeral 1, 2, or 3; and m represents the numeral 0, 1, M2; with the proviso that m+m=3; and (B) a surface-active alkylated naphthalene mono- .sultonic acid in which at least one alkyl group substituted in the naphthalene nucleus contains at least three carbon atoms and not more than 5 carbon atoms.

7. A process for breaking petroleum emulsions of-the water-in-oil type, characterized by subjecting the emulsion tothe action of a demulsiiy ing agent comprising a product of the kind del- 'rivable by neutralization reaction between (A) a surface-active amine of the formula type (R.C00.CzH4)--\ not more than 32 carbon atoms; m represents the numeral 1 2, or 3; and m represents the numeral 0, 1, or 2; with the proviso thatm+m'=3; and

(B) a surface-active propylated naphthalene more than four propyl radicals substituted in the naphthalene nucleus.

- MELVIN DE GROOTE. ARTHUR F. WIRTEL.

"monosulfonic acid containing at least one and not 

